KR20010022768A - Flame-Resistant Thermostable Polycarbonate ABS Moulding Materials - Google Patents

Abstract

The present invention

A. 5 to 95 parts by weight of aromatic polycarbonate or polyestercarbonate,

B. (B.1) 5 to 95% by weight of one or more vinyl monomers

(B.2) 5 to 95% by weight of at least one graft substrate having a glass transition temperature of less than 10 ° C. and an average particle size (d ₅₀ value) of 0.05 to 5 μm.

1 to 60 parts by weight of one or more graft polymers,

C. 0 to 50 parts by weight of the thermoplastic vinyl copolymer,

D. 0.5 to 20 parts by weight of at least one phosphorus compound of formula (I) and optionally at least one additional phosphorus compound different from the compound of formula (I), and

E. 0.05 to 5 parts by weight of fluorinated polyolefin

It relates to a flame-retardant thermoplastic molding composition containing.

<Formula I>

Description

Flame-Resistant Heat-Resistant Polycarbonate ABS Molding Composition {Flame-Resistant Thermostable Polycarbonate ABS Molding Materials}

EP-A 0 640 655 describes molding compositions composed of aromatic polycarbonates, styrene-containing copolymers and graft polymers, which can be flame retardant using monomers and / or oligomer phosphorus compounds.

EP-A-0 363 608 describes flame retardant polymer mixtures composed of oligomeric phosphates with aromatic polycarbonates, styrene-containing copolymers or graft copolymers as well as flame retardant additives. For example, in many applications, such as molded inner housings, the heat resistance of such mixtures is often unsuitable.

Accordingly, it is an object of the present invention to provide flame retardant polycarbonate / ABS molding compositions having not only excellent heat resistance but also high flame retardancy.

Surprisingly, it has been found that by using the mono- and / or oligo-phosphorus compounds according to the invention, flame retardant molding compositions can be obtained which produce shaped articles having very good mechanical properties and excellent heat resistance.

The present invention relates to polycarbonate / ABS molding compositions which are made flame retardant by phosphorus compounds and which are excellent in mechanical properties, in particular heat resistance.

Therefore, the present invention

A. 5 to 95 parts by weight, preferably 10 to 90 parts by weight, in particular 20 to 80 parts by weight of aromatic polycarbonate or polyestercarbonate,

B. (B.1) 5 to 95% by weight of at least one vinyl monomer, preferably 20 to 60% by weight

(B.2) The glass transition temperature is below 10 ° C., preferably below 0 ° C., in particular below −20 ° C., and the average particle size (d ₅₀ value) is 0.05 to 5 μm, preferably 0.20 to 0.35 μm, especially 0.25 5 to 95% by weight, preferably 40 to 80% by weight of at least one graft substrate which is from 0.30 μm

1 to 60 parts by weight, preferably 1 to 40 parts by weight, in particular 2 to 30 parts by weight, of at least one graft polymer of

C. 0 to 50 parts by weight, preferably 1 to 30 parts by weight, in particular 2 to 25 parts by weight, of thermoplastic vinyl (co) polymer,

D. 0.5 to 20 parts by weight, preferably 1 to 18 parts by weight, in particular 2 to 15 parts by weight of at least one phosphorus compound of formula (I) and optionally further phosphorus compound (s) of formula (II) And

E. 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight, in particular 0.1 to 0.5 part by weight of fluorinated polyolefin

It is to provide a flame-retardant thermoplastic molding composition containing (total weight parts of the A + B + C + D + E is 100).

Where

A is each independently of one another halogen, preferably chlorine and / or bromine, C ₁ -C ₈ alkyl, preferably C ₁ -C ₄ alkyl, in particular methyl, C ₆ -C ₁₀ aryl, preferably phenyl Or C ₇ -C ₁₂ aralkyl, preferably phenyl-C ₁ -C ₄ alkyl, especially benzyl group,

R ¹ , R ² , R ³ and R ⁴ are each, independently of one another, C _5-, which may be optionally halogenated C ₁ -C ₈ alkyl groups, or optionally substituted, respectively, with halogen and / or C ₁ -C ₄ alkyl groups. C ₆ cycloalkyl, C ₆ -C ₂₀ aryl or C ₇ -C ₁₂ aralkyl,

y is 0, 1, 2, 3 or 4,

n is independently of each other 0 or 1, preferably 1,

N is 0.3 to 30,

X is a mononuclear aromatic or polynuclear aromatic group having 6 to 30 carbon atoms except diphenyl.

Component A

Suitable aromatic polycarbonates and / or aromatic polyestercarbonates according to the invention according to component A are known in the literature or can be prepared by methods known in the literature (preparation of aromatic polycarbonates). For example, Schnell "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396, for example for the preparation of aromatic polyestercarbonates see DE-OS 3 077 934).

Aromatic polycarbonates, for example, carbonated diphenols by a phase boundary method, optionally using chain terminators and optionally trifunctional or trifunctional or higher branching agents (e.g. triphenol or tetraphenol). It can be prepared by reacting with a halide, preferably phosgene and / or with an aromatic dicarboxylic acid dihalide, preferably benzene dicarboxylic acid dihalide.

Diphenols for the production of aromatic polycarbonates and / or aromatic polyestercarbonates are compounds of formula (III) or groups of formula (IV) or (V).

Where

A ¹ is a single bond, C ₁ -C ₅ alkylene, C ₂ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO ₂ -Or a C ₆ -C ₁₂ arylene group which can be condensed with a further aromatic ring, optionally containing heteroatoms,

B are each independently of one another C ₁ -C ₈ alkyl, preferably C ₁ -C ₄ alkyl, in particular methyl, halogen, preferably chlorine and / or bromine, C ₆ -C ₁₀ aryl, preferably phenyl , C ₇ -C ₁₂ aralkyl or phenyl-C ₁ -C ₄ alkyl, preferably benzyl group,

x is each independently 0, 1 or 2,

p is 1 or 0,

R ⁵ and R ⁶ are each independently hydrogen or a C ₁ -C ₆ alkyl group, preferably hydrogen, methyl and / or ethyl, which may be selected for each Z,

Z is carbon,

m is an integer from 4 to 7, preferably 4 or 5, provided that R ⁵ and R ⁶ are both alkyl on at least one Z atom.

Preferred diphenols are hydroquinones such as ring-brominated and / or ring-chlorinated derivatives of diphenols, resorcinol, 4,4'-dihydroxydiphenyl, bis- (hydroxyphenyl) -C _1- C ₅ -alkane, bis- (hydroxyphenyl) -C ₅ -C ₆ -cycloalkane, bis- (hydroxyphenyl) -ether, bis- (hydroxyphenyl) -sulfoxide, bis- (hydroxyphenyl) -Ketone, bis- (hydroxyphenyl) -sulfone and α, α-bis- (hydroxyphenyl) -diisopropyl-benzene.

Particularly preferred diphenols are 4,4'-diphenylphenol, bisphenol-A, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -Cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxydi Phenyl-sulfones as well as their dibrominated and tetrabrominated or chlorinated derivatives such as 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro 4-hydroxyphenyl) -propane or 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane.

Especially preferred is 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol-A).

Diphenols can be used individually or in any mixture.

Diphenols are known in the literature or can be prepared by methods known in the literature.

Examples of chain terminators suitable for the preparation of thermoplastic aromatic polycarbonates include phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol as well as according to DE-OS 2 842 005. Long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) -phenol or 3,5-di-tert-butyl-phenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol And monoalkylphenols or dialkylphenols having 8 to 20 carbon atoms in total, such as 2- (3,5-dimethylheptyl) -phenol and 4- (3,5-dimethylheptyl) -phenol. The amount of chain terminators used is generally from 0.5 mol% to 10 mol% relative to the molar sum of the diphenols used in each case.

The weight average molecular weight M _w of the thermoplastic, aromatic polycarbonate (as measured by ultracentrifugation or light scattering, for example) is 10,000 to 200,000, preferably 20,000 to 80,000.

Thermoplastic aromatic polycarbonates are branched by known methods, in fact by incorporating 0.05 to 2.0 mole% (based on the sum of the diphenols used) of trifunctional or trifunctional or higher trifunctional compounds, for example compounds having three or more phenolic groups. Can be.

Homopolycarbonates or copolycarbonates are suitable. For the preparation of the copolycarbonates according to component A of the invention, 1 to 25% by weight, preferably 2.5 to 25% by weight of polyorganosiloxanes containing hydroxy-aryloxy end groups (diphenols used Can be used as the total amount of. They are known (see, eg, US Pat. No. 3 419 634) or can be prepared by methods known in the literature. The preparation of polyorganosiloxane-containing copolycarbonates is described, for example, in DE-OS 3 334 782.

Preferred polycarbonates in addition to bisphenol-A homopolycarbonate are bisphenol-A and other preferred diphenols, in particular 15 moles of 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane Up to% (by molar sum of diphenols) copolycarbonate.

Preferred aromatic dicarboxylic acid dihalides for the production of aromatic polyestercarbonates are the diacids of isophthalic acid, terephthalic acid, diphenylether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. Dichloride.

It is especially preferred that the ratio of the mixture of diacid dichloride of isophthalic acid and terephthalic acid is from 1:20 to 20: 1.

When preparing polyestercarbonates, carbonate halides, preferably phosgene, can be used as the bifunctional acid derivatives.

Chain terminators suitable for the production of aromatic polyestercarbonates in addition to the above-mentioned monophenols include aliphatic C ₂ as well as acid chlorides of chlorinated carbonates and aromatic monocarboxylic acids which may be optionally substituted with C ₁ -C ₂₂ alkyl groups or halogen atoms. -C ₂₂ mono-carboxylic acid chloride is also present.

The amount of chain terminators is from 0.1 to 10 mole percent, based on moles of diphenols for phenolic chain terminators and moles of dicarboxylic acid dichlorides for monocarboxylic acid chloride chain terminators.

Aromatic hydroxycarboxylic acids can also be incorporated into aromatic polyestercarbonates.

Aromatic polyestercarbonates can be straight or branched by known methods (see DE-OS 2 940 024 and DE-OS 3 007 934 in each case).

As branching agents can be used in the amounts mentioned: trifunctional or trifunctional or higher carboxylic acid chlorides, for example trimesic acid trichloride, cyanuric trichloride, 3,3 '-, 4,4'- Benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride 0.01 to 1.0 mol% (based on dicarboxylic acid dichloride used) or trifunctional or Trifunctional or higher phenols such as phloroglucine, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene, 4,4-dimethyl-2, 4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl)- Ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis- [4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4 -Hydroxyphenyl-isopropyl) -phenol, tetra -(4-hydroxyphenyl) -methane, 2,6-bis- (2-hydroxy-5-methylbenzyl) -4-methyl-phenol, 2- (4-hydroxyphenyl) -2- (2, 4-dihydroxyphenyl) -propane, tetra- (4- [4-hydroxyphenyl-isopropyl] -phenoxy) -methane, 1,4-bis [(4,4'-dihydroxytriphenyl) -Methyl] -benzene 0.01 to 1.0 mol% (based on diphenols used). Phenolic branching agents first start with diphenols; Acid chloride branching agents may begin with acid dichloride.

The proportion of carbonate structural units in the thermoplastic aromatic polyester carbonates can vary arbitrarily.

The carbonate group content is preferably at most 100 mol%, in particular at most 80 mol% and most preferably at most 50 mol%, based on the sum of the ester groups and the carbonate groups.

The ester and carbonate fractions in aromatic polyestercarbonates may be in the form of blocks or randomly distributed in the polycondensate.

The relative solution viscosity (η _rel ) of the aromatic polyestercarbonates is 1.18 to 1.4, preferably 1.22 to 1.3 (measured in a solution of 0.5 g of polyestercarbonate in 100 ml of methylene chloride at 25 ° C.).

The thermoplastic aromatic polycarbonates and polyestercarbonates can be used individually or in any mixture with one another.

Component B

Component B according to the invention is a graft polymer. These are rubber-elastic graft copolymers substantially obtainable from two or more of the following monomers: chloroprene, 1,3-butadiene, isopropene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and (Meth) acrylates having 1 to 18 carbon atoms of the alcohol component; ie, for example, "Methoden der organischen Chemie" (Houben-Weyl), Volume 14/1, Georg Thieme-Verlag, Stuttgart 1961, p. 393-406 and C.B. Bucknall, "Toughened Plastics", Appl. Science Publishers, London 1977. Preferred polymers B are partially crosslinked and contain a gel content of at least 20% by weight, preferably at least 40% by weight and in particular at least 60% by weight.

Preferred graft polymer B is

B.1 (B.1.1) 50 to 99 parts by weight of styrene, α-methylstyrene, halogen or methyl ring-substituted styrene, methyl methacrylate or mixtures of these compounds, and

(B.1.2) 1 to 50 parts by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, C ₁ -C ₄ alkyl- or phenyl-N-substituted maleic acid imide or mixtures thereof

5 to 95 parts by weight, preferably 30 to 80 parts by weight of a mixture comprising

B.2 5 to 95 parts by weight, preferably 20 to 70 parts by weight, of a polymer based on dienes and / or alkyl acrylates and having a glass transition temperature of less than -10 ° C.

Graft polymer.

Examples of preferred graft polymers B are base B.2 grafted with styrene and / or acrylonitrile and / or alkyl (meth) acrylates, such as polybutadiene, butadiene / styrene copolymers and acrylate rubbers, again Copolymers of the type described in DE-OS 1 694 173 (= US-PS 3 564 077); Polybutadiene grafted with alkyl acrylates or alkyl methacrylates, vinyl acetate, acrylonitrile, styrene and / or alkyl styrenes as described in DE-OS 2 348 377 (= US-PS 3 919 353) , Butadiene / styrene or butadiene / acrylonitrile copolymer, polyisobutene or polyisoprene.

Examples of particularly preferred polymers B are, for example, ABS as described in DE-OS 2 035 390 (US-PS 3 644 574) or DE-OS 2 248 242 (= GB-PS 1 409 275). Polymer.

Particularly preferred graft polymer B is

As α graft B.1, 10 to 70% by weight, preferably 15 to 50% by weight, in particular 20 to 40% by weight of one or more (meth) acrylates (based on graft polymer B); Or from 10 to 50% by weight of acrylonitrile or (meth) acrylate, preferably from 20 to 35% by weight (based on the mixture) and 50 to 90% by weight of styrene, preferably 65 to 80% by weight (based on the mixture). 10 to 70% by weight of the mixture, preferably 15 to 50% by weight, in particular 20 to 40% by weight

β graft base B.2, comprising 30 to 90% by weight, preferably 50 to 85% by weight, in particular 60 to 80% by weight, of butadiene polymer having at least 50% by weight of butadiene groups relative to β (based on graft polymer B) Obtainable by graft reaction with

The gel content of the graft base β is preferably 70% by weight or more (measured in toluene), the graft degree G is 0.15 to 0.55, and the average particle diameter d ₅₀ of the graft polymer B.2 is 0.05 to 2 μm, Preferably it is 0.1-0.6 micrometer.

(Meth) acrylate (alpha) is ester of acrylic acid or methacrylic acid, and the monohydric alcohol of C1-C18. Particular preference is given to methyl, ethyl and propyl methacrylate, n-butyl acrylate, t-butyl acrylate and t-butyl methacrylate.

The graft base β is an ester of acrylic acid or methacrylic acid having 1 to 4 carbon atoms of styrene, acrylonitrile, alcohol component in addition to butadiene group (e.g., methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate). Groups of other ethylenically unsaturated monomers such as vinyl esters and / or vinyl ethers. Preferred graft base β consists only of polybutadiene.

Graft Degree G is the weight ratio of grafted monomers to graft substrate and is dimensionless.

The average particle diameter d ₅₀ refers to the diameter in which 50% by weight of the particles are present above and below the value, respectively. This can be determined by ultracentrifugation measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-796).

Examples of particularly preferred polymers B are

τ. 20 to 90% by weight of acrylate rubber (based on component B) having a glass transition temperature of less than -20 ° C as graft base B.2 and

δ. 10 to 80% by weight of at least one polymerizable ethylenically unsaturated monomer as graft monomer B.1 (based on component B)

Graft polymer.

The acrylate rubber τ in the polymer B is preferably a polymer of up to 40% by weight (based on τ) of the polymerizable ethylenically unsaturated monomer, optionally different from the alkyl acrylate. C ₁ -C ₈ -alkyl esters such as, for example, methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogenated alkyl esters, such as chloroethyl acrylate, preferably halogenated C ₁ -C ₈ alkyl esters, and mixtures of these monomers are preferred polymerizable acrylates.

For crosslinking products, monomers having one or more polymerizable double bonds may be copolymerized. Preferred examples of the crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms with unsaturated monovalent alcohols having 3 to 12 carbon atoms or saturated polyols having 2 to 20 carbon atoms having 2 to 4 OH groups, such as ethylene glycol dimethacryl Late, allyl methacrylate; Polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; Polyfunctional vinyl compounds such as divinylbenzene and trivinylbenzene; As well as triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethylacrylate, diallyl phthalate and heterocyclic compounds having three or more ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are cyclic monomers triallyl cyanurate, triallyl isocyanurate, trivinyl cyanurate, triacryloylhexahydro-s-triazine, triallylbenzene.

The amount of crosslinking monomer is preferably 0.02 to 5% by weight, in particular 0.05 to 2% by weight relative to the graft base τ.

In the case of cyclic crosslinking monomers having three or more ethylenically unsaturated groups, it is advantageous to limit the amount of graft base τ to less than 1% by weight.

Examples of preferred "other" polymerizable ethylenically unsaturated monomers other than acrylates which may optionally be used to prepare the graft base τ are acrylonitrile, styrene, α-methylstyrene, acrylamide, vinyl C ₁ -C ₆ alkyl Ether, methyl methacrylate, butadiene. Preferred acrylate rubbers as graft base τ are emulsion polymers having a gel content of at least 60% by weight.

Further suitable graft substrates according to B.2 include graft-active sites such as those described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539. It is with silicone rubber.

The gel content of graft base B.2 is measured in dimethylformamide at 25 ° C. (M. Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, George Thieme-Verlag, Stuttgart 1977).

Graft polymer B can be prepared by known methods such as bulk, suspension, emulsion or bulk-suspension processes.

As is known, in the graft reaction, the graft monomers do not necessarily have to be completely grafted on the graft substrate, so that the graft polymer B according to the present invention is obtained by polymerization of the graft monomer in the presence of the graft substrate. It means the product which becomes.

The average particle diameter d ₅₀ refers to the diameter in which in each case 50% of the particles are present above and below that value. This can be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloide, Z. and Z. Polymere 250 (1972), 782-1796).

As is known, the graft polymer B according to the present invention can be prepared by (co) polymerization of the graft monomer in the presence of the graft base since graft monomers cannot be completely grafted onto the graft substrate in the graft reaction. Product obtained and present after any treatment.

Component C

Component C comprises at least one thermoplastic vinyl (co) polymer.

Suitable polymers as (co) polymers C include vinyl aromatic compounds, vinyl cyanides such as unsaturated nitriles, C ₁ -C ₈ -alkyl (meth) acrylates, unsaturated carboxylic acids as well as derivatives of unsaturated carboxylic acids ( For example, anhydrides and imides).

C.1 vinyl aromatic compounds and / or ring-substituted vinyl aromatic compounds (eg styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or C ₁ -C ₄ -alkyl Methacrylate (eg, methyl methacrylate, ethyl methacrylate) 50 to 99 parts by weight, and

C.2 vinyl cyanide (unsaturated nitrile) such as acrylonitrile and methacrylonitrile and / or (C ₁ -C ₈ ) -alkyl (meth) acrylates (eg methyl methacrylate) , n-butyl acrylate, t-butyl acrylate) and / or unsaturated carboxylic acids (eg maleic acid) and / or derivatives of unsaturated carboxylic acids (eg anhydrides and imides) ( Particular preference is given to, for example, (co) polymers made from 1 to 50 parts by weight of maleic anhydride and N-phenylmaleic acid imide).

The (co) polymer C is dendritic, thermoplastic, and rubber-free.

Particular preference is given to copolymers of C.1 styrene and C.2 acrylonitrile.

The (co) polymers according to C are prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) polymer according to component C preferably has a weight average molecular weight M _w (determined by the light scattering method or the sedimentation method) of 15,000 to 200,000.

The (co) polymers according to component C are by-products during the graft polymerization of component B, especially when large amounts of monomer B.1 are grafted onto small amounts of rubber B.2. The amount of C which can optionally be used according to the invention does not include such by-products from the graft polymerization of B.

When component C is present in the molding composition, the weight ratio of component B: C should be 2: 1 to 1: 4, preferably 1: 1 to 1: 2 in order to obtain the desired mechanical properties for the particular purpose.

Component D

The molding composition according to the invention contains at least one organophosphorus compound of the formula (I) as a flame retardant.

<Formula I>

Wherein R ¹ , R ² , R ³ , R ⁴ and A and n and y are as defined above. The aromatic groups R ¹ , R ² , R ³ and R ⁴ and A may be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C ₁ -C ₄ -alkyl groups. Particularly preferred aryl groups are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and their corresponding brominated and chlorinated derivatives.

N may have an average value of 0.3 to 30, preferably 0.3 to 20, particularly preferably 0.5 to 10, most preferably 0.5 to 6. When a mixture of phosphorus compounds is present, N may have the above average value. Monophosphorus compounds and / or oligomer phosphorus compounds may be contained in this mixture. When N = 0, formula (I) represents a compound that is mono.

Some of the compounds D may be substituted (up to 75% by weight) with one or more monophosphorus and / or oligoyne and / or polyphosphorus compounds of the formula (II), different from the compounds of the formula (I).

<Formula II>

Wherein R ¹ , R ² , R ³ , R ⁴ , n and N are as defined above.

In the formula (II), X means a mononuclear aromatic or polynuclear aromatic group having 6 to 30 carbon atoms except diphenyl. This group is derived from diphenols according to formula (III), such as bisphenol-A, resorcinol or hydroquinone or their chlorinated or brominated derivatives.

Mixtures of phosphorus compounds of formula (I), preferably monophosphates and / or oligomeric phosphates of formula (I) with N values of 0.5 to 10, in particular 0.5 to 6, are preferably used as component D.

The monomeric and oligomer phosphorus compounds of the formula (I) in the mixture are preferably selected to produce a synergistic effect. The mixture generally consists of 10 to 90% by weight of the compound which is an oligomer of formula (I) and 90 to 10% by weight of the compound which is mono. The monomeric phosphorus compound and / or monophosphate compound are preferably mixed in an amount of 12 to 50% by weight, preferably 14 to 40% by weight, in particular 15 to 40% by weight, in an auxiliary amount of the oligomeric phosphate compound.

Suitable monophosphorous compounds (ie, N = O) include tributylphosphate, tris- (2-chloroethyl) phosphate, tris- (2,3-dibromopropyl) phosphate, triphenyl phosphate, tricresyl phosphate, di Phenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) phosphate, halogen substituted aryl phosphates, dimethyl methyl phosphate, diphenyl methyl phosphate, diethyl phenyl phosphate, Triphenylphosphine oxide and / or tricresylphosphine oxide.

Phosphorus compounds according to component D are generally known organic compounds or can be prepared by methods analogous to known methods (see, eg, Ullmanns Encyklopadie der technischen Chemie, Vol. 18, page 301 et seq. 179; Houben-Weyl, Methoden der organischen Chemie, Vol. 12/1 page 43; Beilstein Vol. 6, page 177).

Component E

Fluorinated polyolefins E are polymers and have a glass transition temperature of at least −30 ° C., generally at least 100 ° C., and generally their fluorine content is from 65 to 76% by weight, in particular from 70 to 76% by weight, with an average particle diameter d ₅₀ of 0.05. To 1,000, preferably 0.08 to 20 μm. In general, the fluorinated polyolefin E has a density of 1.2 to 2.3 g / cm ³ . Preferred fluorinated polyolefins E are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymers and ethylene / tetrafluoroethylene copolymers. Fluorinated polyolefins are known ("Vinyl and Related Polymers" by Schildknecht, John Wiley & Sons, Inc., New York, 1962, pp. 484-494; "Fluorpolymers" by Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Vol. 13, 1970, pp. 623-654; "Modern Plastics Encyclopedia", 1970-1971, Vol. 47, No. 10A, October 1970, McGraw-Hill, Inc., New York, Pp. 134 and 774; "Modern Plastics Encyclopedia", 1975-1976, October 1975, Vol. 52, No 10A, McGraw-Hill, Inc., New York, pages 27, 28 and 472, and US-PS 3 671 487 , 3 723 373 and 3 838 092).

They form free radicals such as sodium persulfate, potassium or ammonium at known methods, for example at 7 to 71 kg / cm ² in an aqueous medium and at a temperature of 0 to 200 ° C., preferably at 20 to 100 ° C. It can be prepared by polymerizing tetrafluoroethylene using a catalyst (see, eg, US Pat. No. 2, 393 967 for more details). Depending on the form of use, the density of these materials may be between 1.2 and 2.3 g / cm ³ and the average particle size may be between 0.5 and 1,000 μm.

Preferred fluorinated polyolefins E according to the invention are tetrafluoroethylene polymers, having an average particle diameter of 0.05 to 20 μm, preferably 0.08 to 10 μm and a density of 1.2 to 1.9 g / cm ³ , and tetrafluoroethylene polymer E Preference is given to use in the form of a coagulation mixture of an emulsion of and an emulsion of graft polymer B.

Suitable fluorinated polyolefins E, which can be used in powder form, are tetrafluoroethylene polymers having an average particle diameter of 100 to 1,000 μm and a density of 2.0 g / cm ³ to 2.3 g / cm ³ .

To prepare a coagulation mixture of B and E, first an aqueous emulsion of graft polymer B (latex) is mixed with a finely divided emulsion of fluorinated polyolefin E; Emulsions of suitable fluorinated polyolefins usually have a solids content of 30 to 70% by weight, in particular 50 to 60% by weight, preferably 30 to 35% by weight.

The data for amounts in the description of component B do not include the proportion of the graft polymer in the coagulation mixture of the graft polymer and the fluorinated polyolefin.

In the emulsion mixture, the weight ratio of graft polymer B to fluorinated polyolefin E is 95: 5 to 60:40. The emulsion mixture may be prepared by known methods, such as spray drying, freeze drying, or preferably of inorganic or organic salts, acids, bases or water miscible organic solvents such as alcohols or ketones at temperatures of 20 to 150 ° C., in particular 50 to 100 ° C. It solidifies by the coagulation method by addition. If necessary, drying may be carried out at 50 to 200 ° C, preferably 70 to 100 ° C.

Suitable tetrafluoroethylene polymer emulsions are commercially available products and are provided, for example, under the trade name Teflon 30N by DuPont.

The molding compositions according to the invention may contain one or more of conventional additives, for example lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers and dyes, pigments and / or reinforcing materials. Suitable inorganic reinforcements are reinforcements in the form of glass fibers, glass beads, glass beads, kaolin, talc, mica, carbon fibers, optionally chopped or ground. It is preferable to use chopped or crushed glass fibers having a length of 1 to 10 mm and a diameter of less than 20 μm in the amount of 1 to 40 parts by weight as the reinforcing material; It is preferable to surface-treat a glass fiber.

In addition, the molding composition according to the present invention is a finely divided inorganic powder, at least one element selected from the group consisting of oxygen, sulfur, boron, phosphorus, carbon, nitrogen, hydrogen or silicon, and groups 1A to 5A or 1B to 8 subgroups of the periodic table. It may contain one or more polar compounds of at least one metal of. Oxides or hydroxides, preferably TiO ₂ , SiO ₂ , SnO ₂ , ZnO, boehmite, ZrO ₂ , Al ₂ O ₃ , iron oxides, mixtures thereof and doped compounds, especially average particle diameters of less than 200 nm, preferably Boehmite or TiO ₂ of 0.1 to 100 nm, in particular 1 to 50 nm, is preferably used as the polar compound.

The molding compositions according to the invention may contain one or more additional flame retardants, optionally synergistic. Examples of further flame retardants include decabromobisphenylethers, organic halogen compounds such as tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine-formaldehyde resins, inorganic such as Mg or Al hydroxide Inorganic compounds such as hydroxide compounds, antimony oxide, barium metaborate, hydroxy-antimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate and tin oxide, as well as siloxane compounds have. Such flame retardants are generally added in amounts of up to 20% by weight relative to the total molding composition.

The molding compositions according to the invention, which contain components A to E and optionally stabilizers, dyes, pigments, lubricants and mold release agents, nucleating agents, nano-particles as well as other known additives such as antistatic agents and reinforcing agents, are known, By mixing and melt-blending or melt-extruding them at temperatures between 200 ° C. and 300 ° C. in conventional apparatus such as internal blenders, extruders and twin screw, wherein component E is in the form of the solidification mixture mentioned above It is preferable to use.

Each of the components can be mixed continuously or simultaneously at about 20 ° C. (room temperature) or at a high temperature by known methods.

The molding compositions of the present invention can be used to make molded articles of any form. Molded articles can in particular be produced by injection molding. Examples of moldings that can be produced are housing parts of any type, for example appliances, such as juicers, coffee machines or mixers, office equipment such as monitors, printers or copiers, cover sheets for use in the construction sector and the automotive sector. For parts. These shaped articles can also be used in the electrical industry because they have very good electrical properties.

The molding compositions are particularly suitable for the production of molded articles requiring high temperature processing in terms of the heat resistance of the plastics used.

A further form of processing is the production of shaped articles by thermoforming of previously prepared sheets or films.

The invention furthermore relates to the use of the molding compositions according to the invention for the production of the molded articles mentioned above in any form, preferably to the molded articles made from the molding compositions according to the invention.

Component A

Bisphenol-A based linear polycarbonate, having a relative solution viscosity of 1.252 measured in CH ₂ Cl ₂ as a solvent at a temperature of 25 ° C. and a concentration of 0.5 g / 100 ml.

Component B

45 parts by weight of a graft polymer composed of styrene and acrylonitrile in a 72:28 ratio grafted onto 55 parts by weight of crosslinked polybutadiene rubber fine particles (average particle diameter d ₅₀ = 0.4 μm) prepared by emulsion polymerization.

Component C

Styrene / acrylonitrile copolymer having a weight ratio of styrene / acrylonitrile of 72:28 and an intrinsic viscosity of 0.55 dl / g (measured in dimethylformamide at 20 ° C.).

Component D

D1

D2 (comparative)

m-phenylenebisdiphenyl phosphate based trade name Fyrolflex RDP (manufactured by Akzo).

Component E

Tetrafluoroethylene polymer as a coagulation mixture formed from a SAN graft polymer emulsion in water according to component C and a tetrafluoroethylene polymer emulsion in water. The weight ratio of graft polymer C to tetrafluoroethylene polymer E in the mixture is 90% by weight to 10% by weight. Tetrafluoroethylene polymer emulsions have a solids content of 60% by weight and an average particle diameter of 0.05 to 0.5 μm. SAN graft polymer emulsions have a solids content of 34% by weight and an average latex particle diameter of 0.4 μm.

Manufacture of E

The emulsion of tetrafluoroethylene polymer (Teflon 30N, DuPont) was mixed with the emulsion of SAN Graft Polymer C and stabilized with 1.8% by weight of phenolic antioxidants relative to the polymer solids. At 85-95 ° C. the mixture was coagulated with an aqueous pH 4-5 solution of MgSO ₄ (Epsom salt) and acetic acid, filtered and washed until practically no electrolyte. Subsequently, most of the water was removed by centrifugation and then the mixture was dried to a powder at 100 ° C. This powder can be combined with other components in the apparatus described above.

Preparation and Testing of Molding Compositions According to the Invention

Components A to E were mixed on a 3 liter internal blender. Molded articles were manufactured by an Arburg 270E injection molding machine at 260 ° C.

Notch impact resistance was measured using a rod of 80 × 10 × 4 mm 3 according to the ISO 180 1A method.

Vicat B softening point was measured according to DIN 53 460.

Stress cracking characteristics were tested using rods of 80 × 10 × 4 kPa dimensions at a bulk temperature of 260 ° C. A mixture of 60% by volume toluene and 40% by volume isopropanol was used as the test medium. Samples were pre-stretched using a template in the form of a circular arc and stored together for 5 or 10 minutes in the test medium at room temperature. The pre-stretch degree δ _x is 0.2 to 2.4%. Stress cracking properties were evaluated by pre-stretch by the production of cracks or fractures.

The composition of the materials tested and the data obtained are summarized in the table below.

Composition and Properties of Polycarbonate / ABS Molding Compositions Example 1 (comparative) 2 3 Ingredients (parts by weight) ABCD1D2E Release Agent 66.77.39.4-12.04.20.4 66.77.39.412.0-4.20.4 66.77.39.414.0-4.20.4 Characteristics: Vicat B ₁₂₀ (℃) Notch Impact Resistance: (KJ / ㎡) ESC-Behavior 10 minutes / 2.4% 5 minutes / 2.4% 5 minutes / 1.6% 9442BR5: 00 11559BR 5:00 11260 No shredding

It can be seen from the table that the molding compositions according to the invention have a very good combination of improved mechanical properties, in particular stress cracking resistance, notch impact resistance and heat resistance.

Claims (14)

A. 5 to 95 parts by weight of aromatic polycarbonate or polyestercarbonate, B. (B.1) 5 to 95% by weight of one or more vinyl monomers (B.2) 5 to 95% by weight of at least one graft substrate having a glass transition temperature of less than 10 ° C. and an average particle size (d ₅₀ value) of 0.05 to 5 μm. 1 to 60 parts by weight of graft polymer, C. 0 to 50 parts by weight of a thermoplastic vinyl (co) polymer, D. 0.5 to 20 parts by weight of a phosphorus compound of formula (I) and optionally at least one further phosphorus compound of formula (II), and E. 0.05 to 5 parts by weight of fluorinated polyolefin Flame retardant thermoplastic molding composition containing (the sum of the weight parts of all the components is 100). <Formula I> <Formula II> Where Each independently of one another is a halogen, or a C ₁ -C ₈ alkyl, a C ₆ -C ₁₀ aryl, or a C ₇ -C ₁₂ aralkyl group, R ¹ , R ² , R ³ and R ⁴ are each, independently of one another, C _5-, which may be optionally halogenated C ₁ -C ₈ alkyl groups, or optionally substituted, respectively, with halogen and / or C ₁ -C ₄ alkyl groups. C ₆ cycloalkyl, C ₆ -C ₂₀ aryl or C ₇ -C ₁₂ aralkyl group, y are each independently of the other 0, 1, 2, 3 or 4, n is each independently 0 or 1, N is 0.3 to 30, X is a mononuclear aromatic or polynuclear aromatic group having 6 to 30 carbon atoms except for diphenyl. The molding composition of claim 1, wherein N in the phosphorus compound of Formula (I) is 0.3 to 20. 3. The compound of claim 1, wherein R ¹ to R ⁴ in formula (I) or (II) may each be optionally substituted independently of each other, C ₁ to C ₄ alkyl group, or halogen and / or alkyl group, respectively. Bisphenol-A, resorcy, which is a C ₆ -C ₁₀ aryl or C ₇ -C ₁₂ aralkyl group and X can be optionally chlorinated, brominated and / or alkylated, except for diphenyl Molding compositions derived from knol or hydroquinone. The compound according to claim 1, wherein the phosphorus compound of formula (II) is tributyl phosphate, tris- (2-chloroethyl) phosphate, tris- (2,3-dibromopropyl) phosphate, Triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri- (isopropylphenyl) phosphate, halogen-substituted aryl phosphates, dimethyl methyl phosphate, Molding composition which is diphenyl methylphosphate, diethyl phenylphosphate, triphenylphosphine oxide or tricresylphosphine oxide. 5. The molding composition according to claim 1, wherein the phosphorus compound of formula (I) and optionally formula (II) is a mixture of compounds having an N average value of 0.5 to 10. 6. The high molecular weight according to any one of claims 1 to 5, wherein the fluorinated polyolefin E has a fluorine content of 65 to 76% by weight, an average particle diameter d ₅₀ of 0.08 to 20 μm, and a density of 1.2 to 2.3 g / cm 3. Molding composition that is a polymer. The molding composition according to claim 1, wherein the molding composition contains 0.01 to 35% by weight of one or more additional flame retardants relative to the total molding composition. The molding composition according to any one of claims 1 to 7, which contains 10 to 90 parts by weight of component A, 1 to 40 parts by weight of component B and 1 to 18 parts by weight of component D. The molding composition according to any one of claims 1 to 8, which contains 20 to 80 parts by weight of component A, 2 to 30 parts by weight of component B, and 2 to 15 parts by weight of component D. The molding composition according to claim 1, wherein the graft base C.2 is a diene rubber, an acrylate rubber, a silicone rubber or an ethylene / propylene / diene rubber. 11. The device according to any one of claims 1 to 10, wherein at least one element selected from the group consisting of elements 1A to 5A or 1B to 8 of the periodic table and oxygen, sulfur, boron, carbon, phosphorus, nitrogen, hydrogen and silicon Molding composition containing the fine powder compound of the. The molding composition according to claim 1, which contains at least one additive from the group of stabilizers, pigments, mold release agents, rheology enhancers, inorganic reinforcements, nano-particles and / or antistatic agents. Use of the molding composition according to any one of claims 1 to 12 for the production of molded articles. Molded article made from the molding composition according to claim 1.